Insoluble heteropolymer of a monoolefin and an unsaturated ether



freezing, inert solvent.

an olefinic ether containing methallyl-allyl ether Patented Dec. 17, 1946 UNITED ATE msowmtmimor OLEFlN AN Ns William -J.1 Sparks, c non, and :Robert 1 N. J assignors to Standard Oil Developmentcompanma corporation otDela-w Thomas, Union,

, ware v No Drawingx Appli TE FF OLYMER on time A UBAf -E EIH R cation J ul y 9,1943,

Serial No.494;,020

. scl n (o1. ace-#86) This application relates to hydrocarbon polymers; relates particularly to interpolymers or heteropolymers of an isoolefinwithL-an oleflnic ether and relates particularly a: heteropolyiners of isobutylene with an oleflnic ether,

As is well known to those skilled in the art, it

ther ethers of higher molecular weight, are

similarly usable, including such :asubstances, was" i -dlvinyl ether, vinyl methallyl ethergetcurwhich contain a two double bonds,

Thus an has been found possibletoproduce a heteropolymer of an isoolefin such as isobutylene with a conjugated diolefin such as butadien or isoprene or the like, utilizingan active metal halide, or Frie'del-Crafts type catalyst dissolved in a low isobutylenewith .an olefinic as in alkadienes-gor adiolefins. i i

prepare a heteropolymer methallyl ether or methallyl-allyl ether and their polymer. Other objects The resulting polymers have molecular weights ranging from 15,000 to I 150,000 and they are reactive with mer is modified and at which the material has a relatively hightensile replaced by an elastic limit strength and a high elongation. This reaction has been found to be very sensitive to added sub- 1 other olefins being strongly poisonous to the reaction, including such substances as isobutylene dimerandvarious other stances, many of the higher unsaturates. Likewise, acid, alkali, alde-;

hyde, ethereal and alcoholic substances have been found to be immediately destructiveto the,

reaction to such an extent that it has been con,- sidered that the presence of oxygenated compounds of any kind is fatal to the reaction; even the aliphatic ethers being, the cause of immediate cessation of the polymersuch substances as erably below 0 C. a A suitable olefinic ether for the present reactionis dimethallyl ether, having the Alternatively, other diolefinic ethers' such as Ha CH3 H2 are usable in the polymerization reaction, still and, in addition, as

sulfur in a e curing reaction by which the fluidity. of the polyis prepared consisting homologues to produce a new tion; i

i In practicing this invention ;anoleflnic miirture C of thesimple olefin, preferably isobutyleneg with a .dioleflnic ether, the

isoolefin being present in anykde'sired proportion;

the isoolefin is present insthe ratio 1 of fromi60 to 99 parts withthediolefl'nic ether butpreferably present in the proportion of 40 to ,l'part. This olefinic mixture may be polymerized at the desired temperature as prepared, only the catalyst i being added; but it is preferably diluted with a diluent-refrigerant such asliquid ethylene or liquid ethane or liquid propane, liquid butane, liquid ethyl or methyl ,chloridesand the like, thefdiluent-re frigerant being present in theproportion of fro'mZ to 5 or fivolumes pervolume of mixed olefins. Alternatively, an excess of solid carbon dioxide may be utilized either with or without an auxiliary diluent such as propane, ride or similar inert,;1ow" freezing substances.

The catalyst preferably consists of a solution b N. 0. Callowa of a dissolved active metal halide, catalyst, pref,- y

formula: I

-' ical Reviews published for ethyl or methyl chloof anactivemetalhalide such asaluminuni chloride, bromide or iodideor uraniumlor titanium chloride, dissolved in a'low freezing solventsuch as ethyl or methyl chloride or carbon-dioxide or similar homologous fs'ubstances. Substantially e any of the Friedel-Crafts catalysts as disclosed in his article on The Frledel- Crafts Synthesis,

cal Societyat Baltimore in the article beginning on page The simple halide compounds may be used or various-forms oi doublesalts such as thechlorobromide and the like-maybe usedl As the catalystsolvent, with the simple Fieclel- Crafts halides, the preferred solvent is a lower alkyl halide, such asethyl or methyl chloride, the alkyl mono or poly object oi the present invention-is to i of ant isoolefln such as ether i'such J as, di-

and useful heteroand details oi the inveni tion will be apparent from the following des'crip- I V methane or mixtures of-one or more of these several ,dilueiit 'refrlgerants, to-

gether with other inert diluents such'asliquid" printed in' the issue of ChenitheAmericanChemi- 1935 in volume XVIII, e

327, the list being I particularly well shown on page 375, may be used.

halides up to 5 or6 carbon volatilized' gaseous constituents.

atoms per molecule which have freezing points below about 0 C., thereby being low-freezing sollarly, a considerable number of the loweiyhyclro- I carbons such as liquid propane, liquid butane and I {the like may be used as solventspapproximately- '7 or:8 carbon atoms compounds being the upper 'limit.' l I o. The temperatureof the reaction for the poly- Q 'merization preferably lies between 0 C. .and

,- about 164 C.; and the most convenient tem p'eratures are -78 CL, asset by solid carbon dioxide, or 95 to 103 C., as set by liquid ethylene. l

Y The catalyst solution may be applied to the reaction mixture in any. desired manner. It

' maybe poured in and'stirred vigorously, provid- "inggithestirring equivalent ,is ,suiiiciently powerful. Ittmay be delivered into-the rapidlystirred reaction mixture as a rapi stream, or by otherv l. methods which will be obvious;'but the catalyst solution is preferably applied 'in the form of a spray or'mist'on to the surface of. the rapidly stirred niixtureof. theolefins and diluent-refrig- "I'he'reaction-proceeds rapidly to produce erant.

the desiredsolid, plastic, elastic polymer.

"Ihe'resulting heteropolymer shows characteristics depending to a large extent upon the y; particular diolefinicetherutilized. A heteropolymer containing substantial proportions of dimethallyl etherlireacts with sulfur, with difficulty: and is strongly resistant to hydrocarbon solvents; The presence of substantial proportions of oxygen as introduced through the diimethallyl ether makes. the material still more strongly resistant to solution in hydrocarbon solvents. V I

'- Example I I mixture of 98 Darts of'l llid isobutylene was prepared w'ith two parts or dimethallyl ether,

and 4 volumes of liquid ethylene were added to ,the 'mixture. lThe mixture was prepared in a reactor, equipped with a powerful stirring device and provided with acover to avoid loss .of

also was well heat insulated to reduce the rate of volatilization of the'refrigerant by ambient heat. The catalyst was prepared by; dissolving commercial anhydrous. aluminum chloride in methyl chloride at'the boiling point or the methyl chloride to yield .a saturatedsolution containing 0.9% 'of aluminum chloride. This solution was then diluted with an additional amount of methyl chloride to produce a solution containing 0.4% of dissolved aluminum chloride, This solution was then precooled to the temperature of the liquid ethylene, approximately 103 C.,

a and sprayed on to the surface of the vigorously stirred mixed olefins through a misting nozzle.

The polymerization proceeded rapidly and was approximately 80% complete in about 5 minutes.

When'this stage of polymerization was reached, the polymerization "mixture was diluted with approximately "volume of propyl alcohol or.

ethyl alcoholor ethyl ether or similar oxygenated hydrocarbon, to quench the catalyst and arrest polymerization. The solid polymer was then brought up'to room temperature and was'ready for furthertprocessing.

This material, as so polymerized, shows a molecular weight ranging from 10,000 to 100,000,

; 'dr'oc'a'rbon and. oxygenated solvents.

The reactor depending upon the temperature, of polymerize tion and the proportion of dimethallyl ether insoluble in ether, alcohol or acetone, and in fact,

"'most}. oxygenated solvents, although again it swells somewhat'by absorption of these solvents.

-'Ihis part icular polymer is poorly reactive with sulfur and does not undergo any curing reaction readily. r

I Example II A similar polymerization reaction is foundto 'occur with methallyl-allyl ether, using similar proportions of the isobutylene and methallyl-allyl ether and a similar polymerization procedure to that abovedisclo'sed'in Example I. In this instance also, a high molecular weight polymer is produced which, however, diifers fromthe polymer of Example I in beingreactive with sulfur for acuring reaction to develop'an elastic limit, a relatively high tensile strength and a high elongation, togetherwith insolubility in both hy- Ezrample III I The heteropolymer of isobutylene and methallyl-allyl ether was then compounded according ,}to the following formula:

I Parts H eteropolymer 100 :Zlncoxide-.. 5 Stearic acid 3 Sulfur Tuads (tetramethyl thiuram disulfide) 1 mpound, the'heteropolymer was, worked briefly upon the mill for a time interval of. approximately 5 minutes.

In preparing this co the mill. Thereafter, the stearic acid and sulfur were simultaneously added, the mill temperature lby weight of isobutylene, .30 parts by weight or divinyl ether and 2000 part by weight of methyl chloride. This material was cooled to a temperature of approximately --78 C. by the addition of 4000 parts by weight of polymerized solid'carbon dioxide.

The material was well stirred and when the temperature had been lowered to the desired point, a steady, moderately rapid streamthe polymer was found to contain approximately 12% of copolymerized divinyl ether. The material showed a good solubility in oil and in light Then the zinc oxidewasadded and thoroughly incorporated into the polymer by further working on s naphtha solvents and when dissolved in a good lubricating oil, produced a substantial improvement in the viscosity index thereof.

Example V A mixture was prepared consisting of 500 parts of isobutylene and 500 parts or divinyl ether. To this mixture there were then added 2000 parts of 'methyl chloride and the material was cooled to a temperature of approximately -'l8 C. by the addition of 4000 parts by weight pulverized solid carbon dioxide. As in Example IV, the polymerization was conducted by bubbling a stream of gaseous boron trifiuoride through the oleflnic material. The polymerization proceeded rapidly to yield a hard polymer which was insoluble in hydrocarbons generally but thermoplastic and suitable for molding operations. The material showed a much greater toughness, and a lower brittleness than is characteristic of polyvinyl ether, and an absence of the cold flow which is characteristic of simple polyisobutylene.

Example VI 2000 parts by weight of a 0.5% solution of aluminum chloride in ethyl chloride were added with rapid stirring of the cold oleflnlc mixture. This procedure yielded a solid polymer which was found to be soluble in hydrocarbons, thermoplastic and excellent for pressure molding.

Many other simple oleflns such as propylene, which contains 3 carbon atoms per molecule, the various normal butylenes, the amylenes and various of the higher oleiins up to about 8 carbon atoms per molecule are similarly reactive with the olefinic ether.

Thus the invention provides a new and useful heteropolymer of an olefin with a diolefinic ether in which relatively high insolubility in solvents generally is obtained, together with Sulfurizability, high strength, high elongation and so forth.

While there are above disclosed but a limited number of embodiments of the invention, it is possible to produce still other embodiments without departing from the inventive concept herein disclosed, and it is, therefore, desired that only such limitations be imposed upon the appended claims as are stated therein orrequired by the prior art.

The invention claimed is:

1 6 50 to 98 parts by weight of an olefin having 3 to 5 carbon atoms and one ethylenic double bond per molecule with 2 to 50 parts by weight of an l. A heteropolymer comprising in combination ether having 4- to 8 carbon atoms and two isolated ethylenic double bonds per molecule, the ether having an oxygen link between hydrocarbon groups containing each of the two isolated ethylenic double bonds.

2. A heteropolymer comprising in combination 98 parts by weight of isobutylene with 2 parts by weight of an ether having an oxygen link between a methallyl group and a, hydrocarbon group containing 3 to 4 carbon atoms and one ethylenic double bond.

3. A heteropolymer comprising in combination 98 parts by weight of isobutylene with 2 parts by weight of dimethallyl ether.

4. A heteropolymer comprising in combination 98 parts by weight of isobutylene with 2 parts by weight of methallyl-ally] ether.

5. A heteropolymer comprising in combination 50 parts by weight of isobutylene with 50 parts by weight of divinyl ether.

6. A composition of matter comprising in combination with sulfur a sulfurizable heteropolymer of 98 parts by weight of isobutylene combined with 2 parts by weight of methallyl-allyl ether.

7. A polymerization process comprising the steps in combination of mixing 50 to 98 parts by weight of a mono-olefin having 3 to 5 carbon atoms per molecule with 50 to 2 parts by weight of an ether having 4 to 8 carbon atoms and two isolated ethylenic double bonds per molecule, the ether having an oxygen link between hydrocarbon groups containing each of the two isolated ethylenic double bonds, cooling the mixture of the monoolefin and the ether to a polymerization temperature between 0 C. and l64 C., and efiecting polymerization of the resulting mixture by adding thereto a Friedel-Crafts catalyst dissolved in an inert organic solvent which is: liquid at the polymerization temperature.

8. A polymerization process comprising the steps in combination of mixing 98 parts by weight of isobutylene with 2 parts by weight of an ether having an oxygen link between a methallyl group and a hydrocarbon group containing 3 to 4 carbon atoms and one ethylenic double bond, cooling the isobutylene mixed with the ether in the presence of liquid ethylene at a polymerization temperature within the range C. to 103 C., and effecting polymerization of the isobuty1- one with the ether in the resulting cooled mixture by adding thereto aluminum chloride in an alkyl halide solvent which is liquid at the polymerization temperature.

WILLIAM J. SPARKS. ROBERT M. THOMAS. 

